Selective Heck Arylation of Cyclohexene with Homogeneous and Heterogeneous Palladium Catalysts 英文参考文献.docVIP

Molecules 2010, 15, 2166-2177; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Selective Heck Arylation of Cyclohexene with Homogeneous and Heterogeneous Palladium Catalysts Ewa Mieczyńska and Anna M. Trzeciak * Faculty of Chemistry, University of Wroc?aw, 14 F. Joliot-Curie, 50-383 Wroc?aw, Poland; E-Mail: gosia@wchuwr.pl (E.M.) ? Author to whom correspondence should be addressed; E-Mail: ania@wchuwr.pl; Tel.: +48 71 3757253; Fax: +48 71 3282348. Received: 27 January 2010; in revised form: 10 March 2010 / Accepted: 23 March 2010 / Published: 25 March 2010 Abstract: Palladium catalysts containing Pd(II) supported on Al2O3 and alumina-based mixed oxides, Al2O3-ZrO2, Al2O3-CeO2, and Al2O3-Fe2O3, are very effective in the Heck coupling of iodobenzene with cyclohexene in DMF solution. The best results, up to 81% of monoarylated products with a selectivity to 4-phenylcyclohexene (3) close to 90% were obtained with KOH as a base. The catalytic activity of palladium supported on alumina- based oxides was compared with that of homogeneous precursors, such as Pd(OAc)2 and PdCl2(PhCN)2, used in [Bu4N]Br as the reaction medium. Under such conditions homogeneous systems were more selective and produced up to 60% of monoarylated products with a selectivity to 3 close to 60%. Keywords: palladium; Heck coupling; heterogenized catalysts; cyclohexene 1. Introduction The Heck coupling, a C–C bond formation process also described as olefin arylation, is one of the most important palladium-catalyzed reactions [1–6]. Arylated olefins, the final products of the Heck reaction, have very broad application in the synthesis of pharmaceuticals, agrochemicals, and natural products. Therefore, very intensive research has been addressed to the development of new, simple and efficient catalytic systems for the Heck coupling.  Molecules 2010, 15 2167 Typical palladium cataly